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While gas-phase synthesis techniques offer a scalable approach to production of metal nanoparticles, directed assembly is challenging due to fast particle diffusion rates that lead to random Brownian aggregation. This work explores an electromagnetic-levitation technique to generate metal nanoparticle aggregates with fractal dimension (Df) below that of diffusion limited assembly. We demonstrate that in addition to levitation and induction heating, the external magnetic field is sufficient to compete with random Brownian forces, which enables the formation of altered fractals. Ferromagnetic metals (Fe, Ni) form chain-like aggregates, while paramagnetic Cu forms compact nanoparticle aggregates with higher Df values. We have also employed a Monte Carlo simulation to evaluate the necessary field strength to form linear chains in the gas phase.

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Unlike liquid phase colloidal assembly, significantly changing the structure of fractal aggregates in the aerosol phase, is considered impractical. In this study, we discuss the possibility of applying external magnetic and electric fields, to tune the structure and fractal dimension (Df) of aggregates grown in the aerosol phase. We show that external fields can be used to induce dipole moments in primary nanoparticles. We found that an ensemble of particles with induced dipole moments will interact through directional attractive and repulsive forces, leading to the formation of linear, chain-like aggregates with Df ~ 1. The aggregate structure transition is dependent on the primary particle sizes, temperature and applied field strength which was evaluated by performing a hybrid ensemble/cluster-cluster aggregation Monte Carlo simulation. We demonstrate that the threshold magnetic field strength required to linearly assemble 10-500 nm particle sizes are practically achievable whereas the electric field required to assemble sub-100 nm particles are beyond the breakdown strength of most gases. To theoretically account for the enhanced coagulation rates due to attractive interactions, we have also derived a correction factor to both free molecular and transition regime coagulation kernel, based on magnetic dipolar interactions. A comparison has been made between the coagulation time-scales estimated by theory and simulation, with the estimated magnetization time-scales of the primary particles along with oscillation time period of the magnetic field, to demonstrate that sub-50 nm superparamagnetic primary particles can be magnetized and assembled at any temperature, while below the Curie temperature ferromagnetic particles of all sizes can be magnetized and assembled, given the applied field is higher than the threshold.

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We develop an approach for computing the hydrodynamic friction tensor and scalar friction coefficient for an aerosol fractal aggregate in the transition regime. Our approach involves solving the Bhatnagar-Gross-Krook equation for the velocity field around a sphere and using the velocity field to calculate the force on each primary sphere in the aggregate due to the presence of the other spheres. It is essentially an extension of Kirkwood-Riseman theory from the continuum flow regime to the entire Knudsen range (Knudsen number from 0.01 to 100 based on the primary sphere radius). Our results compare well to published direct simulation Monte Carlo results, and they converge to the correct continuum and free molecule limits. Our calculations for clusters with up to 100 spheres support the theory that aggregate slip correction factors collapse to a single curve when plotted as a function of an appropriate aggregate Knudsen number. This self-consistent-field approach calculates the friction coefficient very quickly, so the approach is well-suited for testing existing scaling laws in the field of aerosol science and technology, as we demonstrate for the adjusted sphere scaling method.

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We apply our extended Kirkwood-Riseman theory to compute the translation, rotation, and coupling friction tensors and the scalar rotational friction coefficient for an aerosol fractal aggregate in the transition flow regime. The method can be used for particles consisting of spheres in contact. Our approach considers only the linear velocity of the primary spheres in a rotating aggregate and ignores rotational and coupling interactions between spheres. We show that this simplified approach is within approximately 40% of the true value for any particle for Knudsen numbers between 0.01 and 100. The method is especially accurate (i.e., within about 5%) near the free-molecule regime, where there is little interaction between the particle and the flow field, and for particles with low fractal dimension (≲2) consisting of many spheres, where the average distance between spheres is large and translational interaction effects dominate. Our results suggest that there is a universal relationship between the rotational friction coefficient and an aggregate Knudsen number, defined as the ratio of continuum to free-molecule rotational friction coefficients.

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An approach to obtain the mobility of nonspherical particles is proposed by averaging the drag force orientationally, and two other widely used approaches in the literature, the averaged-collision-integral and averaged-drift-velocity methods, are summarized and extended. The concept of orientationally averaged collision integrals based on Chapman-Enskog theory for small gas-phase ions is re-examined for macromolecular ions whose surface cannot be treated as specular, but with inelastic interactions. A well accepted collision model considering inelastic collisions is Epstein's theory, which has been extended to include long-range potential forces by Li and Wang [Phys. Rev. E 68, 061206 (2003)] for spherical particles. This work extends Li and Wang's spherical particle theory to convex nonspherical particles considering long-range potential, and simplifies this collision integral to a product of the averaged projection area and an enhancement factor for short-range interactions (hard collisions), which is independent of convex particle shape and is identical to the value for a sphere that people are using. We also show that the averaged projection area of a convex particle in free molecular regime for hard collisions is equal to its mobility diameter. The second approach is the averaged-drift-velocity approach using the friction coefficient in a tensor form, which is often employed in aerosol science. We extend this approach in our previous work for axisymmetric particles to develop an expression for the mobility of nonspherical particles in a general form. Furthermore, it is pointed out that this approach is only valid when the particle Brownian rotation is slow compared with the particle translational relaxation time. If the particle Brownian rotation is fast, usually so in the case of very small ions and particles, we propose an "averaged-drag-force" approach. The three approaches are then compared for a randomly oriented rod and the protein GroEL. We show that for a cylinder rod in the free molecular regime at random orientation, the averaged-drag-force approach is identical to the averaged-collision-integral approach for short-range interactions (hard collisions). We then summarize the relationship between collision-integral based approach and tensor based approaches. For readers only interested in implementation of the theory, we provide useful expressions in Tables I and II.

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We benchmark the performance of a photoacoustic spectrometer with a calculable cell constant in applications related to climate change measurements. As presently implemented, this spectrometer has a detection limit of 3.1 × 10(-9) W cm(-1) Hz(-1/2) for absorption by a gas and 1.5 × 10(-8) W cm(-1) Hz(-1/2) for soot particles. Nonstatistical uncertainty limited the accuracy of the instrument to ∼1%, and measurements of the concentration of CO(2) in laboratory air agreed with measurements made using a cavity ring-down spectrometer, to within 1%. Measurements of the enhanced absorption resulting from ultrathin (<5 nm), nonabsorbing coatings on nanoscale soot particles demonstrate the sensitivity of this instrument. Together, these measurements show the instrument's ability to quantitatively measure the absorption coefficient for species of interest to the climate and atmospheric science communities. Because the system constant is known, in most applications the acoustic response of this instrument need not be calibrated against a sample of known optical density, a decided advantage in field applications. Routine enhancements, such as improved processing of the photoacoustic signal and higher laser beam power, should further increase the instrument's precision and sensitivity.

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The peak particle size and expanded uncertainties (95 % confidence interval) for two new particle calibration standards are measured as 101.8 nm ± 1.1 nm and 60.39 nm ± 0.63 nm. The particle samples are polystyrene spheres suspended in filtered, deionized water at a mass fraction of about 0.5 %. The size distribution measurements of aerosolized particles are made using a differential mobility analyzer (DMA) system calibrated using SRM(®) 1963 (100.7 nm polystyrene spheres). An electrospray aerosol generator was used for generating the 60 nm aerosol to almost eliminate the generation of multiply charged dimers and trimers and to minimize the effect of non-volatile contaminants increasing the particle size. The testing for the homogeneity of the samples and for the presence of multimers using dynamic light scattering is described. The use of the transfer function integral in the calibration of the DMA is shown to reduce the uncertainty in the measurement of the peak particle size compared to the approach based on the peak in the concentration vs. voltage distribution. A modified aerosol/sheath inlet, recirculating sheath flow, a high ratio of sheath flow to the aerosol flow, and accurate pressure, temperature, and voltage measurements have increased the resolution and accuracy of the measurements. A significant consideration in the uncertainty analysis was the correlation between the slip correction of the calibration particle and the measured particle. Including the correlation reduced the expanded uncertainty from approximately 1.8 % of the particle size to about 1.0 %. The effect of non-volatile contaminants in the polystyrene suspensions on the peak particle size and the uncertainty in the size is determined. The full size distributions for both the 60 nm and 100 nm spheres are tabulated and selected mean sizes including the number mean diameter and the dynamic light scattering mean diameter are computed. The use of these particles for calibrating DMAs and for making deposition standards to be used with surface scanning inspection systems is discussed.

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Experimental measurements of laser-induced ionization were performed for ethene-air premixed flames operated near the soot inception point. Soot was ionized with a pulsed laser operated at 532 nm. The ionization signal was collected with a tungsten electrode located in the postflame region. Ionization signals were collected by use of both single-electrode and dual-electrode configurations. Earlier laser-induced-ionization studies focused on the use of a single biased electrode to generate the electric field, with the burner head serving as the path to ground. In many practical combustion systems, a path to ground is not readily available. To apply the laser-induced-ionization diagnostic to these geometries, a dual-electrode geometry must be employed. The influence of electrode configuration, flame equivalence ratio, and flame height on ionization signal detection was determined. The efficacy of the laser-induced-ionization diagnostic in detecting soot inception in the postflame region of a premixed flame by use of a dual-electrode configuration was investigated. Of the dual-electrode configurations tested, the dual-electrode geometry oriented parallel to the laser beam was observed to be most sensitive for detecting the soot inception point in a premixed flame.

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The slip correction factor has been investigated at reduced pressures and high Knudsen number using polystyrene latex (PSL) particles. Nano-differential mobility analyzers (NDMA) were used in determining the slip correction factor by measuring the electrical mobility of 100.7 nm, 269 nm, and 19.90 nm particles as a function of pressure. The aerosol was generated via electrospray to avoid multiplets for the 19.90 nm particles and to reduce the contaminant residue on the particle surface. System pressure was varied down to 8.27 kPa, enabling slip correction measurements for Knudsen numbers as large as 83. A condensation particle counter was modified for low pressure application. The slip correction factor obtained for the three particle sizes is fitted well by the equation: C = 1 + Kn (α + ß exp(-γ/Kn)), with α = 1.165, ß = 0.483, and γ = 0.997. The first quantitative uncertainty analysis for slip correction measurements was carried out. The expanded relative uncertainty (95 % confidence interval) in measuring slip correction factor was about 2 % for the 100.7 nm SRM particles, about 3 % for the 19.90 nm PSL particles, and about 2.5 % for the 269 nm SRM particles. The major sources of uncertainty are the diameter of particles, the geometric constant associated with NDMA, and the voltage.

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The polarization and intensity of light scattered by polystyrene latex and copper spheres with diameters of approximately 100 nm deposited onto silicon substrates containing various thicknesses of oxide films were measured with 532-nm light. The results are compared with a theory for scattering by a sphere on a surface, originally developed by others [Physica A 137, 209 (1986)] and extended to include coatings on the substrate. Nonlinear least-squares fits of the theory to the observations yield results that were consistent with differential mobility measurements of the particle diameter.

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The polarization and intensity of light scattered by monodisperse polystyrene latex and copper spheres, with diameters ranging from 92 to 218 nm, deposited on silicon substrates were measured with 442-, 532-, and 633-nm light. The results are compared with a theory for scattering by a sphere on a surface, originally developed by others [PhysicaA 137,209 (1986)], and extended to include coatings on the sphere and the substrate. The results show that accurate calculation of the scattering of light by a metal sphere requires that the near-field interaction between the sphere and its image be included in acomplete manner. The normal-incidence approximation does not suffice for this interaction, and the existence of any thin oxide layer on the substrate must be included in the calculation.

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Smoke agglomerates are made of many soot sphcres, and their light scattering response is of interest in fire research. The numerical techniques chiefly used for theoretical scattering studies are the method of moments and the coupled dipole moment. The two methods have been obtained in this tutorial paper directly from the monochromatic Maxwell curl equations and shown to be equivalent. The effects of the finite size of the primary spheres have been numerically delineated.

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The intensity of the light scattered from individual dielectric spheres was measured as a function of the scattering angle, for light polarized parallel and perpendicular to the scattering plane. These sets of data were used to determine the radius and refractive index of the spheres by fitting the data to the scattering function obtained from Mie theory. The light was produced by a He-Cd laser (λ=441.6 nm). Measurements were performed on particles of six discrete sizes with radii in the range 117-1175 nm. Several different measures of the quality of fit were examined, and the least-squares fit, unweighted or weighted with a factor sin2(θ/2), was found to be the best. The values obtained for the index of refraction were found to be within 1% of the published bulk value 1.615. The measured radii differed by several percent from those specified by the manufacturer. Several sources of error were analyzed, and their effects were simulated in numerical experiments. The largest source of error in the instrument was a discrepancy between the actual scattering angle and the reading provided by the instrument. Less significant was the noise introduced by the motion of the particle within the laser beam. A calibration eliminated most of the error in the scattering angle. The precision and accuracy of this technique are estimated to be 0.2% and 0.9%, respectively, of the particle size for particles of a nominal radius of 457 nm.